Method of manufacturing elastic sealing material



Aug. 17, 1954 J, w. WURTZ EI'AL 2,686,747

METHOD OF MANUFACTURING ELASTIC SEALING MATERIAL Filed March 24, 1950 JOHN W. WURTZ AND FRED A. GREENWALD m 'E.\'TOR.

y M/AVQQ ATTYI Patented Aug. 17, 1954 UNITED STATES PATENT OFFICE METHOD OF MANUFACTURING ELASTIC SEALING MATERIAL John W. Wurtz, San Gabriel, and Fred Alton Greenwald, South Gate, Calif., assignors to National Motor Bearing 00., Inc., Redwood City, Calif. a corporation of California ApplicationMarch 24, 1950, Serial No. 151,766

6 Claims. (01. 154-84) caused ordinary sealing materials to become em- 1 brittled and hardened. Thus; in the sealing of airplane cabins, it is desirable that the sealing material maintain its elasticity at temperatures as low as -60 F. to 80 F., which are encountered at high altitudes. The same material must also withstand temperatures at low altitudes varying from 100 F. to 150 F. at some seasons to as high as 200 F to 300 F. at otherseasons.

Rubber and similar materials heretofore in use were unsatisfactory.

We have provided a satisfactory sealing product for this service from an elastic organic silicone compound formed into a cellular structurecr sponge. For this purpose we prefer toyuse the rubber like polymethyl alkylsiloxanes retained in a suitable jacketing material for support and to prevent abrasion of the relatively Weak polysiloxanecompound. Previous attemptsto use this material in solid form for sealing purposes have been unsuccessful owing to the low resilience of thepolysiloxanes, resulting in serious deformation under prolonged stress. We have solved this problem by incorporating inert-gases in the polysiloxane in a cellular structure as hereinafter described. Methods heretofore in use in conned tion with the manufacture of cellular rubber products were found unsatisfactory when applied to the polysiloxanes; so the new method of this invention had to be devised.

The invention is described in a drawing which shows in Figure 1 partly in perspective and in cross section a typical form of seal employed for sealing the openings in airplane cabins operating at high altitudes under pressurized conditions. Figure 2 is a cross-section of a similar seal product in modified form.

In the preparation of our sealing material we may employ polyethyl siloxane, polyisopropyl siloxane, et cetera, but we prefer to employ polymethyl siloxane whichis an elastomer marketed in various grades under thenamej oi Silastic. To this material we add about to 2% of an expanding agent which may suitably be a thermally sensitive organic diazo or nitroso compound; for example, we may add about l %of diazoaminobenzene. Thorough mixing is obtained by milling on squeeze rolls or by other suitable mixing device. The temperature of mixing should not be permitted to rise above ordinary temperatures; for example to F; Instead of the nitrogen compound We may use other expanding agents capable of disengaging gases when heated. so- .dilllll bicarbonatafor example, can be employed.

in some cases where a high rate of heating is. employed in the expanding step, to be hereinafter described, the dissolved gases in the Silastic.

are sufficient to effectthe desired expansion without addition of any expanding. agent.

A curing agent for the polysiloxane is also required. For this purpose various oxidizing agents are used, preferablyorganio peroxidessuch as benzoyl peroxide, aoetyl peroxida diethyl peroxy dicarbonate et cetera in amounts of about 0.1 to 5 g.

After uniformly incorporating the expanding agent, the Silastic combination is next formed into approximately the desiredshape, for example, by extruding through a die. Thus wemay form it into rods or tubes. The resulting extruded product is next heated to activate the expanding agent, thereby forming the polysiloxane into a sort of sponge and greatly increasing its compressibility. Itis usually sufficient to heat to a temperature of about 250 to 550 for about five to twenty-five minutes. When employing diazoamino benzene a temperature of 400* F.

for a period of ten minutes is usually sufiicient.

ber product now in the form of a soft sponge is covered to provide resistance to abrasion and to increase its strength and general applicability. For this purpose it is preferred to employ a fabric comprised of glass fiber or. nylon because of the great strength and durability of these materials and their stability at the required curing ternperatures. It is desirable to cement the cover to the polysiloxane sponge by means of a polysiloxane cement which is suitably a dispersion of i partially polymerized methylsiloxane in a solvent such as xylene or tetrachlor ethylene. If desired, the covering fabric may be completely impregnated with the cement to increase its durability. Other cements such as Vinylite and rubber, suitably in theform of an emulsion or latex, may be employed but are less desirable because of their lower chemical stability and greater susceptibility to hardening in use at low temperatures.

The drawing shows a section of a sealing material prepared in the form of a. cylinder or rope with a web for convenience in fastening. The spongy polysiloxane body It is surrounded by a flexible sheathing ll which is brought together in a seam at E2 and formed into a web l3. A layer of cement it attaches the spongy polysiloxane core to the cover which is usually fabric.

After the fabric sheath has been applied to the polysiloxane sponge, the product is subjected to heat in a curing oven usually for about 4 to 12 hours at a temperature of about 300 to 500 F. for the purpose of curing the polysiloxane sponge and preventing it from collapsing under long sustained pressure and deformtaion. The curing treatment also serves to set the Silastic cement employed in attaching the sheath to the core.

In another modification of our invention, we inject the unexpanded composition of polyalkylsiloxane rubber and expander into a suitable sheath before the initial expanding heat treatment, thereby expanding it directly in place. When carried out in this way, the process permits expanding and curing the material in a single heating operation which usually extends for a period of 4 to 12 hours at a temperature of from 300 to 550 F. It is sometimes advantageous when operating in this way to effect the initial expansion at a higher temperature, for example 450 F. and then lower the temperature to 350 F. and hold at that temperature for the remainder of the curing time. According to this modification of the process, the polysiloxane composition containing the expander, id est diamino-azobenzene, can be extruded directly into the sheath in an amount sufficient to slightly more than fill the volume of the sheath on expansion. The sheath may be initially coated on the inside with a suitable cement to provide a firm bond between the sheath fabric and the polysiloxane sponge. Various bonding agents as heretofore described can be employed. However, the use of a bonding agent is not obligatory when operating in this manner inasmuch as there is a tendency for the polysiloxane to become self bonded to the sheath fabric on expansion. Still other types of flexible sheath material use no fabrics at all. For example, we may employ for this purpose an elastic tube of neoprene (polychloroprene) or Buna rubber. In this case it is necessary to insert the cured polysiloxane sponge into the sheath, generally after coating with suitable cement; for example rubber cement or polyvinyl acetate cement to facilitate assembly. If desired, the rubber may be initially expanded by treating with a light hydrocarbon such as benzene or hexane. On evaporation of the hydrocarbon after assembly, the sheath can be shrunk onto the polysiloxane core and the two parts may then be bonded by heating in an oven or autoclave to a temperature sufficient to soften the thermoplastic cement previously applied to the intervening surfaces.

In another modification of our product, a sheath material of polysiloxane film or tubing 4 may be applied to the surface of the; polysiloxane rubber sponge; for example, by cementing and wrapping or by intrusion as just hereinabove described. Formation of the sponge Within a dense polysiloxane tubular sheath may also be effected by expanding in situ.

It is usually desirable to incorporate one or more inorganic modifying agents or extenders in These inorganic modifying agents generally increase the hardness of the resulting cellular polysiloxane product and reduce excessive flexibility Where that is desirable; For this purpose we may employ zinc'oxide, alumina gel, bauxite, fullers earth, any of the numerous forms of iron oxide or ferric oxide such as ochre, rouge, umber, titanium oxide andsilica gel. When employing silica gel, we prefer to use the alcogel because of its extremely low density. All of the above inorganic extenders are employed in a finely divided form, generally having a particle size in the range of about 1 to 30 microns. The amount of inorganic extender may vary from about 5 to 40%, usually about 10 to 25%.

In addition to those materials hereinabove dewire B5. A strip of thin sheet brass, copper,

aluminum or zinc may be employed and, if desired, it may be perforated to facilitate fastening. The use of a deformable soft metal strip or wire in the web either completely enclosed or cemented to one face thereof permits the shaping of the sealing material to a form which Will be retained during handling.

If desired we may soften the sponge poly siloxane rubber material by squeezing, for example through rollers, after the initial cure and beforethe final hardening treatment. We prefer to crush the sponge material sufficient to rupture or break a major part of the cell structure, then apply the sheath and proceed with the final heat treatment. The softened product suffers less distortion in the final heating owing to escape of gases from the ruptured cells, and the bond to the sheath is not damaged by expansion.

The product of the invention is characterized by the unique property of maintaining a high degree of compressibility and elasticity over a long period of time and over a wide range of temperatures from about F. to upwards of +400 F. We have found that the gases trapped in the cells of polysiloxane are retained much more persistently than in the case of other elastic materials attempted to be used for this purpose. We believe that the outstanding advantage of our product is due partially to the low rate of diffusion of gases such as nitrogen, oxygen, air and carbon dioxide through the cellular structure of our expanded polysiloxane. that the incorporation of the expanded poly siloxane material within a sheath resistant to the passage of gases such as cemented or impregnated glass or nylon fabric or within a sheath of rubber, Silastic, neoprene, Buna N, Buna S or other elastomer serves to still further maintain the compressibility of our product and prevent collapse over a long period of time when employed as a We believe further sealing agent under conditions where the material is greatly deformed by compressive forces.

Having thus described our invention, what we claim is:

1. The method of making a highly compressible elongated sealing material having a high resistance to permanent deformation and char acterized by high retention of its elastic properties at temperatures below 100 F. which comprises incorporating into a polysiloxane elastomer about to 2% of an expansion agent capable of liberating an inert gas when heated, extruding the resulting composition in the form of an elongated core of relatively small cross section, subjecting said extruded core to heating to a temperature of about 250 to 550 F. whereby the polysiloxane is expanded into multicellular form, rupturing the cell walls so that the cells interconnect and are exposed to the atmosphere, cementing to the resulting multicellular polysiloxane core an abrasion resistant sheath stable to heating at 500 F. and thereafter subjecting the resulting assemblage to the action of heat at a temperature in the range of about 300 to 500 F. for a period of about 4 to 12 hours to cure the expanded polysiloxane core.

2. A method of making Weatherstrip material suitable for sealing closures in airplane cabins which are subjected to a wide variation in temperature, said method comprising the. steps of: (a) compounding an organic polysiloxane elastomer with a setting agent and an expanding agent capable of liberating an inert gas when heated; (b) preforming the stated elastomer mixture into a shape approximating the desired final shape; heating the shaped material to expand it to its final shape in a multicellular condition; (d) crushing said expanded material so as as to rupture the cell walls, interconnect the cells, and expose them to the atmosphere; (e) bonding the resulting polysiloxane sponge inside an abrasion-resistant sheath; and (f) curing said sponge within said sheath by subjecting it to further heating.

3. The method of claim 2 in which the expansion heating step (c) is conducted at temperatures between about 250 F. to about 550 F. for about 5 to 25 minutes, and the curing heating step (f) is conducted at temperatures between about 300 F. and about 500 F. for about 4 to 12 hours.

4. A method for making a sealing material that Will flex over a wide range of temperatures from about --100 F. to about +400 F. which includes the following steps: mixing at ordinary room temperatures a silicone rubber, a curing agent for said silicone rubber, fillers, and an expanding agent which gives off an inert gas when heated; forming said mixture into an elongated core; heating said core at about 250 to 550 for about 5 to 25 minutes free of confining molds and other shaping apparatus so that it is free to expand to its own limits as said inert gas is liberated by said expanding agent, thereby producing a structure composed of a large number of isolated cells, each containing said inert gas; crushing the expanded core to rupture the walls of said cells to interconnect them and open them to communication with the outside atmosphere at the ends of said core; cementing the outer walls of said core to a fabric sheath; and then completing the cure of said core within said sheath at an elevated temperature.

5. A method for making Weatherstripping material that will flex at temperatures down to about R, which includes the steps of forming a silicone rubber core into a multicellular, generally-cylindrical sponge containing isolated cells; rupturing the cell walls so as to interconnect said cells; sheathing said core; and curing the sheathed core.

6. The method of making a highly compressible sealing material in elongated form and small cross section applicable to the sealing of closures throughout a wide range of temperatures, which comprises: incorporating an expanding agent into a polysiloxane elastomer; extruding the resultant composition into a flexible tubular sheath in an amount sufiicient to fill said sheath when expanded; subjecting the resultant product to heat sufficient to expand said polysiloxane; rup turing the walls of the cells formed upon the expansion; and continuing the heating operation until the resulting expanded polysiloxane sponge is effectively cured.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,045,234 Willis et al Nov. 26, 1912 1,397,842 Netzel Nov. 22, 1921 1,939,878 Davidson Dec. 19, 1933 1,940,924 Taylor Dec. 26, 1933 1,958,131 Davidson May 8, 1934 2,102,658 Weisenburg Dec. 21, 193'? 2,106,817 Soule Feb. 1, 1938 2,114,308 McGowan et a1 Apr. 19, 1938 2,122,372 Hooper June 28, 1938 2,204,622 Reid June 18, 1940 2,459,721 Poltorak Jan. 18, 1949 2,460,795 Warrick Feb. 1, 1949 2,503,003 Bayonne et al Apr. 4, 1950 2,505,353 Fisk Apr. 25, 1950 2,541,137 Warrick Feb. 13, 1951 2,568,672 Warrick Sept. 18, 1951 FOREIGN PATENTS Number Country Date 490,461 Great Britain Aug. 11, 1938 OTHER REFERENCES Modern Plastics, Dec. 1946, pages 102-104 on Silicone Rubber. 

1. THE METHOD OF MAKING A HIGHLY COMPRESSIBLE ELONGATED SEALING MATERIAL HAVING A HIGH RESISTANCE TO PERMANENT DEFORMATION AND CHARACETERIZED BY HIGH RETENTION OF ITS ELASTIC PROPERTIES AT TEMPERATURES BELOW -100* F. WHICH COMPRISES INCORPORATING INTO A POLYSILOXANE ELASTOMER ABOUT 1/2 TO 2% OF AN EXPANSION AGENT CAPABLE OF LIBERATING AN INERT GAS WHEN HEATED, EXTRUDING THE RESULTING COMPOSITION IN THE FORM OF AN ELONGATED CORE OF RELATIVELY SMALL CROSS SECTION, SUBJECTING SAID EXTRUDED CORE TO HEATING TO A TEMPERATURE OF ABOUT 250* TO 550* F. WHEREBY THE POLYSILOXANE IS EXPANDED INTO MULTICELLULAR FORM, RUPTURING THE CELL WALLS THAT THE CELLS INTERCONNECT AND ARE EXPOSED TO THE ATMOSPHERE, 